Premium
Synthesis and Structural Studies of S P and R P Diastereomers of Deoxyxylothymidyl‐3′‐ O ‐acetylthymidyl (3′,5′)‐ O ‐(2‐Cyanoethyl)phosphorothioate in Solution and in the Solid State
Author(s) -
Potrzebowski Marek J.,
Yang XianBin,
Misiura Konrad,
Majzner Wieslaw R.,
Wieczorek Michal W.,
Kaźmierski Slawomir,
Olejniczak Sebastian,
Stec Wojciech J.
Publication year - 2001
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200104)2001:8<1491::aid-ejoc1491>3.0.co;2-3
Subject(s) - diastereomer , chemistry , pseudorotation , heteronuclear molecule , crystallography , crystallization , absolute configuration , intermolecular force , stereochemistry , hydrogen bond , amorphous solid , molecule , nuclear magnetic resonance spectroscopy , organic chemistry
The synthesis and full assignment of the molecular structure of the diastereomers of deoxyxylothymidyl‐3′‐ O ‐acetylthymidyl (3′,5′)‐ O ‐(2‐cyanoethyl)phosphorothioate ( 1 ) in the liquid phase based on 1 H, 13 C, 1D and 2D homo‐ and heteronuclear PFG (Pulse Field Gradient) NMR spectroscopic experiments are reported. The pseudorotation parameters of deoxyribose and deoxyxylose were analyzed by means of the PSEUROT program. The absolute configuration R P and S P of the phosphorus centers was deduced from 1 H ROESY experiment. The 31 P CP/MAS technique was used to establish the ratio between the amorphous and crystalline phases, and to test the progress of crystallization. The differences in the 31 P δ ii principal elements of the chemical shift tensor, in particular the δ 33 parameter, for crystalline and amorphous phases were calculated. Finally, the X‐ray data for the S P diastereomer are reported. The influence of weak C−H ··· S hydrogen bonding on the molecular packing of both R p ‐ 1 and S P ‐ 1 , and the significance of this type of intermolecular interaction for phosphorothioate systems is discussed.